Chemical composition



Patented Dec. 3, 1935 UNITED STATES.

CHEMICAL COMPOSITION Benjamin R. Harris, Chicago, 111.

No Drawing. Application November 10, 1933, Serial No. 697,533

21 Claims.

My invention relates to new chemical compositions and methods ofproducing the same.

My present invention is a continuation in part of my prior applicationSerial No. 431,964, filed February 27, 1930.

In many of the arts, there is a demand or need for materials having ingeneral an oleaginous or fatty character but as well certaincharacteristics not ordinarily associatedwith fats. Thesecharacteristics may, in general, be summed up in the term hydrophyllicproperty. This hydrophyllic property, however, is merely a broadgeneralization, as in different cases the characteristic is identifiedwith the particular object or function desired in the art or industry.

The principal object of the present invention is the provision of a newcomposition of matter adapted for use in various arts.

Another object is the provision of a process for producing suchmaterials.

The materials of my invention are in general esters of polyglycerols andrelatively high molecular weight fatty acids with free OH groups. In thepreferred practical form of the invention,

the material is a mixture of various chemical compounds, all havingoleaginous and aqueous properties imparted to them by the character ofgroups present in the molecule. The lipophile group may be modified butthe hydrophile group is an OH group and through the number of the OHgroups definite hydrophyllic character is present. The material is, ingeneral, a mixture of various polyglycerides with or without thepresence of some portions of mono-glycerides in the form of monoordi-esters. Further consideration of the character of the material willbe shown from the following description in which the method of makingthe materials is set out.

the preferred form of producing my materials, I first produce thepoly-glycerols by the treatment of glycerine with a small amount ofalkali under suitable conditions. As an example, I take 10 pounds ofglycerine containing practically no water or as little water aspossible, and heat the same with of a pound of sodium hydroxide. Thetemperature is brought up to about 260 C., and heating is continued forabout four and one-half hours, preferably in a non-oxidizing atmosphere.I preferably bubble carbon dioxide or some other inert gas through theglycerine while raising the temperature and preferably before theintroduction of the sodium hydroxide.

During the prolonged heating, the water formed as a reaction productboils off with small-portions of glycerine. The result of the process isthe formation of polyglycerols. In the particular manner in which Icontrol the process, a mixture of various polyglycerols is obtained. Itshould be noted that the higher the temperature employed, 5 the longerthe heating period, and the stronger the alkali, the greater will be thedegree of polymerization. The reverse is true as well. For my purpose,the degree of polymerization obtained in the example given is verysatisfactory. 10 It will be understood that even in my preferredprocess, other forms of alkali may be used in place of the sodiumhydroxide. As an example, I have produced very good results by the useof potassium hydroxide, magnesium oxide, sodium 15 carbonate, sodiumacetate, and other equivalents. In each case, however, somemodification, either in time of treatment, temperature, or amount ofalkali, is necessary to obtain comparative results. Infurther steps ofthe process, the mixture of poly-glycerols is reacted under' suitableconditions with higher fatty acids to produce the mixture of esterspreferred in my product. In general, I employ an excess of thepolyglycerols in order to "obtain a final product having the desiredsuitable hydrophyllic character. As a source of fatty acids, I mayemploy substantially any, of the usual fats and oils of commerce. Thecharacter of the final product is best understood by a consideration ofsome examples for 39 producing the same.

Example 1 I take 675 parts of coconut oil, 800 parts of polyglycerolprepared as above, and .675 pound 35 of caustic soda employed as acatalyst. The materials are mixed together and heated with continuedstirring until a temperature of about 250 C. is attained. The materialsare retained at this temperature and constantly stirred forapproximately two hours, preferably in the absence of air. As in theabove described method 'of producing the polyglycerols, air may bereplaced with an inert gas and this is readily accomplished by--bubbling, for example, carbon dioxide or nitrogen through the mixture.The resulting product is then cooled and is found to be a thick, heavyviscous mass having pronounced fatty characteristics insofar as itsordinary appearance and behavior is concerned. It has a pronouncedaqueous character, however, in thatit is miscible with or dispersible inwater in substantially all pro-. portions. Investigation shows that theproduct is a mixture which contains a very large proportion of mixedpolyglycerol esters with free OH groups. If desired, the composition maybe neutralized or even rendered slightly acid and it will still befreely dispersible in water. Its behavior, however, will be slightlymodified by the neutralizing treatment, the amount of modificationdepending upon how much acid is added to it.

Example 2 I take 300 pounds of neats foot oil, and mix the same with 300pounds of polyglycerol prepared as above, and of a pound of causticsoda. The mixture is heated for three hours at a temperature ofapproximately 260 to 265 C. in the absence of air and preferably usingthe technique set out in connection with Example 1. The material isallowed to settle after cooling and the excess of polyglycerol found tobe present is drawn off. The resulting product is a thick, viscous darkbrown oil which, however, emulsifies very readily with water.

Example 3 300 pounds of corn oil is heated with 300 pounds ofpolyglycerol prepared as above at approximately 265 C. in the presenceof of a pound of caustic soda. The same technique may be employed as inpreceding examples and, as in Example 2, the unreacted portion ofpolyglycerol is drawn ofi. The resulting product is a viscous dark brownoily liquid readily emulsiflable with water.

Example 4 540 pounds of prime leaf lard is mixed with 640 pounds ofpolyglycerols prepared as described, and 54/100 pound of caustic sodaadded thereto. The mixture is heated to approximately 260 C. andmaintained at this temperature for approxi mately three hours. Anon-oxidizing atmosphere is maintained and the material is stirredconstantly during heating. After cooling, the excess of polyglycerol isdrawn off. The resulting product is a lard-like fatty composition which,however, is readily dispersible in water and/or other aqueous medium.

Example 5 In place of carrying out the step of polymerizing theglycerine completely before employing the second step of the process, Imay continue to carry on the polymerizing step in conjunction withesteriflcation as it occurs in the second step of the process. As anexample, I take 3% parts of sodium hydroxide (flaked) and dissolve thesame in 325 parts of glycerine The solution is heated in a non-oxidizingatmosphere to 260 C. This requires some time because of the wateroriginally present which has to boil off, and also because of the waterof reaction which must also be expelled. After the temperature isreached, I continue to heat with constant stirring for about two andone-half hours. At this time, 400 pounds of melted oleostearine and 4/10 part of caustic soda are added. Heating is continued in an inertatmosphere at a temperature between 240 and 250 C. The mixture becomeshomogeneous appr-aximately in this temperature range. This temperatureis maintained for about one and one-half hours or more, and the mass isthen cooled while maintaining a nonoxidizing atmosphere. The productcomprises a mixture of polyglycerol esters possessing availablecolloidal properties, but differing somewhat from products produced inpreceding examples.

In place of triglycerides and the like, I may employ higher molecularweight fatty acids directly. This will produce a product with somewhatdiiferent characteristics. For example, I may produce a stearic acidester of mixed polyglycerols as follows: 1400 parts of anhydrous glyc- 5erol and 30 parts of fused sodium acetate are mixed and heated at 275 C.in a non-oxidizing atmosphere for five hours. 930 parts of this reactionmixture are then treated with parts of stearic acid and heated withcontinuous agi- 10 tation for sixteen hours at between to 200 C. Theproduct is a tacky solid of a dark color and readily emulsifiable inwater. It is to be noted that in this example, a catalyst is notemployed to hasten the reaction between the poly- 15 glycerols and thefatty reacting material. The above example can be modified in manyrespects. For instance, the time of heating may vary and, of course,other catalysts may be used instead of sodium acetate. 20 I have givenexamples in which polymerization of the glycerine is substantiallycompleted before reesterification, and at least one exampe in which somepolymerization and re-esterification are carried on together. I may asan alter- 25 native carry out the polymerization and re-esterificationby mixing glycerine and the oil or fat together with a catalyst, andheat the mixture with constant stirring. An excess of glycerine isdesirable in this case, and prolonged heating is 30 advisable. The finalproduct, however, will differ from those of the preceding examples,although it will be hydrophyllic and contain a mixture of polyglycerideswith free OH groups.

I have given several examples above of the 85 manner of producing my newcomposition, all employing a natural oil or fat of commerce, whetherhydrogenated, partially hydrogenated, or unhydrogenated. The materialreacted with the polyglycerols, however, instead of being a 40triglyceride may also be a monoor di-glyceride. In fact, substantiallyany wax, fat, or fatty acid, whether occurring naturally orsynthetically produced, can be used as the reacting substance.

The materials produced in accordance with my 45 invention may becompared with substances produced heretofore by sulfonation. It is wellknown that various fats and oils by sulfonation processes have been mademore or less dispersible in water. The sulfonation products, however,are not at all 50 suited for all purposes. The products of my inventionare in many respects exceedingly more oily or fatty in character thancorresponding substances produced by sulfonation and havingsubstantially the same fat radical. In general they disperse much morereadily in water than the products of the prior art referred to. Inother words, the substances of my invention may be considered forms ofsoluble oil. They may be employed to enhance the stability of emulsions,60 are of value in some arts as wetting agents, can be used asdetergents, and in general have a function in many arts in which thisgeneral type of material has been used in the past.

In the process of producing my materials, pro- 65 portions,temperatures, and other factors may be modified "to vary thecharacteristics of the final product. When a tri-glyceride is used suchas coconut oil, the amount of polyglycerol esters formed depends uponthe proportion of the polyglycerols used in the reaction. If a smallamount of polyglycerol is used, a mixture of the monoand di-glyceridesof the fatty acids together with a mixture of the monoand di-fatty acidpolyglycerol esters is obtained. If a larger propor- 75 tion ofpolyglycerol is used, it will replace substantially all of theglyceri'ne esterifled in the fatty substances. My invention includeseither type of material. The composition may be used in the formproduced, may be purified, neutralized, or treated in any way which doesnot aflect its desired characteristics. Where free glycerine is producedin re-esterification of a fat or oil, it may be removed, or where thereis no objection to its presence, it may be allowed to remain in thecomposition.

I may use my products directly, or-purify them to modify or improve theodor, color, or taste, or remove impurities, such as unreacted glycerineor the like by dispersing in hot water and then throwing the substancesout of dispersion by neutral or acid electrolytes.

As an illustration of this method of treating my products; I disperse200 parts of the product obtained in Example No. 4 in 1000 parts of hotwater by warming and stirring until ahomogeneous dispersion is obtained.I then stirin about 50 parts of common salt and allow the mixture toremain at rest until two layers are obtained. The lower layer, that isthe brine layer, with dissolved impurities, may be drawn ofi and whatremains is the purified polyglycerol ester with an appreciablecontent'of water varying between 30 and 50%, depending upon conditions.The water, if desired, may be boiled 011, (amp orated off under vacuum,or otherwise separated from the polyglycerol ester. The recoveredemulsion in the form of a paste, however, may be employed directly andwith some advantage in most of the arts in which my material has a use.

For certain purposes where an extremely pure product is desired, thewashing step may be re-' peated several times, if desired, to remove alltraces of objectionable impurities.

I have previously referred in general to the uses of my materials. Theyhave a place in the arts relating to emulsifying, detergents andlubricating compounds. On account of their high emulsifying value, theycan be used advantageously in the preparation of various cosmetics andhand lotions. They also may be used for wetting or lubricating fibrousmaterials- .They

can be employed in place of'Turkey red oils of commerce forsubstantially any purpose for which Turkey red oils are used, forexample, stuffing leather. They can be used with insecticide sprays asemulsifying assistants. They can be used in paints to reduce thesettling of lakes and pigments. They may be used as assistants inlaundering. They may be added to soap or other detergent materials.They. may be used in connection with compounded lubricating oilemulsions. In all of these uses, they may be employed alone or withalkaline substances, either as a necessary part of a composition or as adispersing agent.

As an example of the use of the material of my invention, I give below aformula for vanishing cream.

Grams Rose water 1400 Glycerine 250 Stearic acid 120 Potassium hydroxide12 Polyglycerol fatty acid ester of Example L, 80

In the conventional formula of which the above is a modification,approximately 300 grams of glycerine would customarily be used. Thecharof my material makes it possible to decrease Lard the amount ofglycerine, this being due in part to the fact that the material when notpurified will contain some free glycerine. In compounding the vanishingcream, the ingredients are warmed and agitated together in a stirringapparatus or colloid 5 mill. The material of my invention preferably isincorporated after the formation of the emulsion.

Other accessory ingredients such as whitening agents, perfume, and thelike can, of course, be added. The finished product will have a goodtexture, greater resistance to syneresis and excellent spreading value.

In making a cosmetic cold cream, I may employ the following formula:

Stearic acid- 1000 grams 150 grams Polyglycerol fatty acid ester of Ex--ample 4 50 grams Ammonia water 100 cc. Distilled water 7700 cc.

The usual auxiliary ingredients such as perfume and the like may beadded to the formula, The emulsion is made in a suitable way at atemperature somewhat above room temperature. The resulting product issuperior to usual creams of commerce in most respects for which thistype of material is used.

Still other examples of emulsions employing my materials are as follows:

This preparation may have coloring material added, if desired.

Kerosene emulsion I Parts Soap 4 Water. 100 Kerosene 90 Mixedpolyglycerides oflilxample 2 10 1 An emulsion of this character may havemany uses in various arts.

Variousother emulsions are improved by the incorporation of thematerials of my invention,

such as shaving and cleaning preparations, insecticides, medicines,germicides, and the like. Cosmetic preparations such as lipsticks androuges can be improved by employing my materials. They may be used, forexample, after the manner disclosed in my prior application, Serial No.407,797, filed November 16, 1929, now Patent No. 1,958,700, and of whichthe present application is a continuation in part.

The above emulsions are purely by way of example, as many'other formulasmay be used in the cosmetic and other arts in which the material of myinvention may be employed either as an emulsifying agent alone, toreplace some of the fatty material ordinarily used in the emulsion, 7

or in other ways which are obvious from the preceding description.

What I claim as new and desire to protect by Letters Patent of theUnited States is:

1. A chemical composition comprising an ester of a polyglycerol and arelatively high molecular weight of'fatty acid, said ester having freeOH groups.

2. A chemical composition comprising esters of mixed polyglycerols and arelatively high molecular weight fatty acid, said esters having free OHgroups.

3. A chemical composition comprising esters of mixed polyglycerols andmixed relatively high molecular weight fatty acids, said esters havingfree OH groups.

4. A chemical composition comprising a reaction product of a mixture of,polyglycerols and a triglyceride, wherein glycerine is'replaced in partor in whole by a polyglycerol, said reaction product having free OHgroups.

5. A chemical composition comprising a reaction product of a mixture ofpolyglycerols and a triglyceride, including fatty acid esters ofglycerine with free OH groups. I

6. A chemical composition comprising a reaction product of a mixture ofpolyglycerols and a naturally occurring oleaginous substance of a classconsisting of oils, fats and waxes, said reaction product having free OHgroups.

7. A chemical composition comprising a mixture of glycerides andpolyglycerides formed by reacting a mixture of polyglycerols withanaturally occurring liquid oil having a fatty acid radical, the productof said composition having free OH groups.

8. A chemical composition comprising a mixture of glycerides andpolyglycerides formed by reacting a polyglycerol andcoconut oil, theprodnot of said composition having free OH groups.

9. The method of producing a new chemical composition which comprisesproducing a mixture of polyglycerols by polymerization of glycerine in anon-oxidizing atmosphere, and reacting said polyglycerols with anoleaginous material having a reactive lipophile radical to produce amixture of polyglycerides having free OH groups.

10. The method of producing a new chemical composition which comprisesmixing polyglycerols with a material having an esteriflable fatty acidradical in the presence of a relatively small amount of alkali as acatalyst, and heating the mixture to react the polyglycerols and fattymaterial and form a mixture of polyglycerides having free OH groups.

11. The method of producing a new chemical composition which comprisesmixing an excess of polyglycerol with a fatty material having anesteriiied fatty acid radical, and heating the mixture to cause areaction and produce a fatty acid ester of polyglycerol having free OHgroups.

12. The method of producing a new chemical composition which comprisesmixing an excess 5 of the polyglycerol with a fatty material having anesterifled fatty acid radical, and heating the mixture in the presenceof a relatively small amount of alkali to cause a reaction and produce afatty acid ester of polyglycerol having free OH groups. 7

13. The method of producing a new chemical composition which comprisesmixing an excess of the polyglycerol with a fatty material having anesterified fatty acid radical, heating the mixture to cause a reactionand produce a fatty acid ester of polyglycerolv having free OH groups,and washing the resulting material in brine to remove impuritiestherefrom.

14. An emulsion of an aqueous liquid and a fatty acid ester ofpoiyglycerol with free OH groups.

15. An emulsion of an aqueous liquid and a mixture of fatty acid estersof polyglycerols with free OH groups. 2.3

16. An emulsion of oleaginous material, an aqueous liquid and aproportion of a fatty acid ester of polyglycerol with free OH groups.

17. An emulsion of oleaginous material, an aqueous liquid, and aproportion of a mixture of fatty acid esters of polyglycerols with freeOH groups. 1

18. An emulsion comprising an aqueous liquid, an oleaginous material,anda reaction product of a mixture of polyglycerols and a triglyceride,said reaction product having free OH groups.

19. An emulsion comprising an aqueous liquid. an oleaginous material, analkaline substance, and a reaction product of a mixture of polyglycerolsand a triglyceride, said reaction product having free OH groups.

20. The method of producing an improved hydrophylllc chemicalcomposition which comprises adding about l% of a relatively strongalkali to glycerine and heating the mixture at a temperature ofapproximately 260 C. for at least four hours until a highly polymerizedproduct is produced, mixing the polymerized product with an oleaginoussubstance of a class consisting of oils, fats, waxes and fatty acids,and heating the mixture to cause re-esteriflcation of fatty acids of theoleaginous material with the highly polymerized glycerine, wherebypolyglycerides having free OH groups are produced.

21. A chemical composition comprising a fatty acid ester of apclyglyceroi, said ester having at least one free OH group.

BENJAMIN R. HARRIS.

DIsOLARMER 2,022,766.Be'n (1min R. Harris, Chicago,

' i5 Disclalmer filed January 7, 1939, by the asslg'nee,

dated ecember 3, 1935. The Emulsol Corporation.

Hereby enters this disclaimer to claims 1 and 21 in said s Ill. CHEMICALCOMPOSITION." Patent ecification.

[Ofiicial Gazette February 28, 1989.]

DISCLAIMER 2,022,-766.Ben'a1m'1t R. Harris, Chicago, Ill. CHEMICALCOMPOSITION. Patent dated fiecember 3, 1935. Disclaimer filed January 7,1939, by the assignee, The Emulsol Corporation. i Hereby enters thisdisclaimer to claims 1 and 21 in said specification. [Qflic'ial GazetteFebruary 28, 1939.]

